CN108707114B - Acetamide compound and preparation method and application thereof - Google Patents
Acetamide compound and preparation method and application thereof Download PDFInfo
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- CN108707114B CN108707114B CN201810415806.5A CN201810415806A CN108707114B CN 108707114 B CN108707114 B CN 108707114B CN 201810415806 A CN201810415806 A CN 201810415806A CN 108707114 B CN108707114 B CN 108707114B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
Abstract
The acetamide compound has a structure shown in a formula I, is a novel bactericide, can be applied to prevention and treatment of diseases in agriculture and forestry, has a good prevention and treatment effect, particularly has a good prevention and treatment effect on cucumber downy mildew, cucumber powdery mildew and soybean rust, has the prevention and treatment effect on the cucumber downy mildew of more than 50% when the concentration of the acetamide compound is 400ppm, has the prevention and treatment effect on the cucumber downy mildew of more than 50% and the prevention and treatment effect on the cucumber powdery mildew of more than 50%, has the prevention and treatment effect on the soybean rust of more than 50%, and is simple and efficient in preparation method, easy for large-scale production and wide in application prospect.
Description
Technical Field
The invention belongs to the field of agricultural bactericides and relates to an acetamide compound as well as a preparation method and application thereof.
Background
Amide fungicides are a commonly used class of fungicides, in which the amount of the fungicide is a considerable proportion, which is of interest for their high biological activity, but which are resistant to diseases after a period of use, and there is a continuing need for new and improved compounds and compositions having fungicidal activity.
CN106831615A discloses an application of 1,2, 3-triazole-5, amide compounds as agricultural fungicides, wherein the 1,2, 3-triazole-5, amide compounds have the following structures:
wherein R is1Is selected from
Or
R2Is selected from
Or
The compound has good antibacterial activity on plant pathogenic bacteria. CN106699732A discloses a bactericidal composition containing pyrazole amide bactericides, the active ingredient of which is
The amide compound and the methoxy acrylate bactericide with the structure are compounded and synergized, so that the control effect on rice sheath blight and damping off is improved.
However, since pests and diseases are easily resistant to bactericides, there is a need in the art to develop a wider variety of bactericides having good bactericidal effects.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an acetamide compound, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an acetamide compound having a structure represented by formula I below:
wherein Q is1Selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, Q2Selected from substituted or unsubstituted aryl, R1Selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkylcarbonyl or substituted or unsubstituted alkoxycarbonyl.
In the invention, the acetamide compound with the structure shown in the formula I has obvious antibacterial activity, belongs to a novel bactericide, and can be applied to prevention and treatment of diseases in agriculture and forestry.
Preferably, the substituent in the substituted aryl or substituted heteroaryl is halogen atom, C1-C6 alkyl, C1-C6 haloalkyl, C1-C7 alkoxy, C1-C7 haloalkoxy, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 cycloalkylmethyl, C3-C6 halocycloalkylmethyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C4 alkylamino, di-C1-C4 alkylamino, cyano, nitro, hydroxyl, phenyl, phenoxy or halophenoxy.
Preferably, the aryl group is phenyl, naphthyl or tetrahydronaphthyl.
Preferably, the heteroaryl group is a pyridyl, pyridine-N-oxy, pyrimidinyl, pyridazinyl, pyrazinyl, furyl, thienyl, quinolyl, tetrahydroquinolyl, benzofuryl or indolyl group.
Preferably, R1Selected from hydrogen, C1-C6 alkyl, C1-C6 alkylcarbonyl or C1-C6 alkoxycarbonyl, more preferably hydrogen, C1-C6 alkyl or C1-C6 alkylcarbonyl.
Preferably, Q2Selected from phenyl or para-substituted phenyl, preferably phenyl, para-fluorophenyl, para-chlorophenyl or para-bromophenyl.
In the present invention, alkyl means straight-chain or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like. Haloalkyl refers to a group in which the alkyl group is substituted with one or more halogen atoms. Alkoxy means a group having an oxygen atom attached to the terminal of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, and the like. Haloalkoxy refers to a group in which an alkoxy group is substituted with one or more halogen atoms. Cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Alkenyl means straight or branched chain alkenyl, such as 1-propenyl or 2-propenyl. Alkynyl means straight or branched chain alkynyl, such as 1-propynyl or 2-propynyl.
In the present invention, C1-C6, C3-C6 and the like before the specific group indicate the number of carbon atoms contained in the group, for example, C1-C6 indicate a group whose number of carbon atoms may be 1,2,3, 4,5 or 6, C3-C6 indicate a group whose number of carbon atoms may be 3,4,5 or 6, C1-C4 indicate a group whose number of carbon atoms may be 1,2,3 or 4, C2-C4 indicate a group whose number of carbon atoms may be 2,3 or 4, and the like.
Preferably, the acetamide compound of the present invention is any one or a combination of at least two of the compounds shown in the following table 1:
TABLE 1
Wherein Me is methyl, Et is ethyl and i-Pr is isopropyl.
As a preferable technical scheme, the acetamide compound provided by the invention is any one or a combination of at least two of the following compounds (the numbers correspond to the compound numbers in the table 1):
in another aspect, the present invention provides a salt of the acetamide compound as described above, including an inorganic salt or an organic salt of the acetamide compound.
Preferably, the inorganic salt comprises any one of hydrochloride, sulfate, nitrate, bicarbonate, carbonate, or phosphate or a combination of at least two thereof;
preferably, the organic salt comprises any one of formate, acetate, trifluoroacetate, benzenesulfonate, p-toluenesulfonate, methanesulfonate, benzoate, citrate, malate, tartrate, maleate, succinate, ascorbate or oxalate, or a combination of at least two thereof.
In another aspect, the present invention provides a method for preparing the acetamide compound described above, the method comprising:
when the acetamide compound is shown as R in the general formula I1When hydrogen is used: reacting a compound shown as a formula II with a compound shown as a formula III to obtain an acetamide compound shown as a formula I-A, wherein the reaction formula is as follows:
wherein LG represents a readily leaving group, preferably a chlorine atom, a bromine atom or an acyloxy group; q1And Q2The definitions of (a) and (b) are as described above and will not be described herein.
Preferably, the molar ratio of the compound of formula II to the compound of formula III is 1:1 to 3:1, such as 1:1, 1.3:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1 or 3: 1.
Preferably, the solvent for the reaction is any one of dichloromethane, chloroform, hexane, carbon tetrachloride, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide or a combination of at least two thereof.
Preferably, the reaction is carried out in the presence of a basic substance, which is an organic or inorganic base.
Preferably, the organic base is any one or a combination of at least two of triethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide.
Preferably, the inorganic base is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride or a combination of at least two of them.
Preferably, the reaction temperature is greater than or equal to-10 ℃ and less than or equal to the boiling point of the reaction solvent, such as-10 ℃, -5 ℃, -3 ℃,0 ℃,3 ℃,5 ℃,8 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or the like, or the reaction is carried out under the condition of solvent boiling point, i.e. reflux.
Preferably, the time of the reaction is 0.5 to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
When the acetamide compound is shown as R in the general formula I1When hydrogen is not present: reacting the acetamide compound shown in the formula I-A with a compound shown in the formula IV to obtain an acetamide compound shown in the formula I-B, wherein the reaction formula is as follows:
wherein LG represents a readily leaving group, preferably a chlorine atom, a bromine atom or an acyloxy group, Q1And Q2The definitions of (a) and (b) are as described above and will not be described herein.
Preferably, the molar ratio of the acetamide compound of formula I-A to the compound of formula IV is 1:1 to 1:3, such as 1:1, 1:1.3, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8 or 1: 3.
Preferably, the solvent for the reaction is any one of dichloromethane, chloroform, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide or a combination of at least two thereof.
Preferably, the reaction is carried out in the presence of a basic substance, which is an organic or inorganic base.
Preferably, the organic base is any one or a combination of at least two of triethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide.
Preferably, the inorganic base is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride or a combination of at least two of them.
Preferably, the reaction temperature is greater than or equal to-10 ℃ and less than or equal to the boiling point of the reaction solvent, such as-10 ℃, -5 ℃, -3 ℃,0 ℃,3 ℃,5 ℃,8 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or the like, or the reaction is carried out under the condition of solvent boiling point, i.e. reflux.
Preferably, the time of the reaction is 0.5 to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
In another aspect, the present invention provides the use of an acetamide compound as described above for the control of plant diseases.
The acetamide compound provided by the invention has a good plant disease control effect.
Preferably, the plant disease is soybean rust, cucumber downy mildew or cucumber powdery mildew.
In another aspect, the present invention provides a bactericide composition comprising an active ingredient which is an acetamide compound or a salt thereof as described above and an agriculturally pharmaceutically acceptable carrier.
The bactericide composition can be used in the fields of agriculture, forestry, sanitation and the like.
Preferably, the active ingredient is present in the fungicide composition in an amount of 1 to 99% by weight, such as 1%, 3%, 5%, 8%, 10%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 99%.
In another aspect, the present invention provides a method for controlling plant diseases, the method comprising: applying an effective dose of the fungicide composition as described above to a medium in which a plant disease or its growth is to be controlled.
Preferably, the effective dose is from 10 to 1000g per hectare, for example 10g, 20g, 50g, 80g, 100g, 120g, 150g, 180g, 200g, 250g, 300g, 350g, 400g, 450g, 500g, 600g, 700g, 800g, 900g or 1000g, preferably from 20 to 500g per hectare.
The composition of the present invention may be applied to the disease or its growth medium in the form of a formulation. The compound of formula I as an active ingredient is dissolved or dispersed in a carrier or formulated so as to be more easily dispersed when used as a bactericide. For example: these chemicals can be formulated as wettable powders or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant may be added.
For certain applications, for example in agriculture, one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizers and the like may be added to the fungicidal compositions of the present invention, thereby providing additional advantages and effects.
Compared with the prior art, the invention has the following beneficial effects:
the amide compound has obvious effect on preventing and treating diseases in agriculture and forestry, especially has good prevention and treatment effect on cucumber downy mildew, cucumber powdery mildew and soybean rust, the prevention and treatment effect on the cucumber downy mildew is more than 50 percent when the concentration of the acetamide compound is 400ppm, the prevention and treatment effect on the cucumber powdery mildew is more than 50 percent, the prevention and treatment effect on the soybean rust is more than 50 percent, and the preparation method is simple, efficient, easy for large-scale production and wide in application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this example, compound 25 as in table 1 above was prepared as follows:
(1) synthesis of 1- (4-chlorophenyl) -3- (2-nitrophenoxy) -1H-pyrazole
To a reaction flask, 1- (4-chlorophenyl) -3-hydroxy-1H-pyrazole (5.85 g, 30.00 mmol), 2-fluoronitrobenzene (4.23 g, 30.00 mmol), DMF (60 ml) and potassium carbonate (4.55 g, 33.00 mmol) were added in this order, and the reaction solution was heated to reflux. After refluxing for 6 hours, the reaction mixture was cooled to room temperature, water (100 ml) was added to the reaction mixture, extraction was performed with ethyl acetate (150 ml), the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 20: 1) to obtain 7.5 g of a white solid with a yield of 79.03%.
(2)2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) -oxy) aniline
To a reaction flask, 1- (4-chlorophenyl) -3- (2-nitrophenoxy) -1H-pyrazole (5.00 g, 15.84 mmol), ethanol (50 ml) and Pd/C (0.50 g) were added in this order, and hydrazine hydrate (3.17 g, 63.35 mmol) was added dropwise to the reaction solution at 0 ℃. After completion of the dropwise addition, the reaction mixture was reacted at room temperature for 2 hours, and then the reaction mixture was filtered, water (100 ml) was added to the filtrate, extraction was performed with ethyl acetate (150 ml), the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 4.10 g of a yellow liquid with a yield of 90.60%.
(3) Preparation of Compound 25
To a reaction flask were added 2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) aniline (0.29 g, 1 mmol), DCM (6 ml), triethylamine (0.13 ml), and o-fluorophenylacetyl chloride (0.17 g, 1 mmol) in this order, and the mixture was stirred at room temperature for 16 hours. Water (50 ml) was added to the reaction mixture, and extraction was performed with DCM (50 ml), and the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.30 g of a yellow solid with a yield of 71.50%.
Process for preparation of Compound 251H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.41(d,1H, J ═ 8.5Hz),7.94(s,1H),7.78(d,1H, J ═ 2.6Hz),7.62 to 7.55(m,2H),7.49 to 7.40(m,2H),7.35 to 7.30(m,2H),7.26 to 7.20(m,1H),7.19 to 7.14(m,2H),7.13 to 6.98(m,3H),3.79(s, 2H).
Example 2
In this example, compound 26 as in table 1 above was prepared in 52.30% yield by a method different from example 1 only in that o-fluorobenzeneacetyl chloride used in step (3) was replaced with o-chlorobenzeneacetyl chloride.
Process for preparation of compound 261H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.39(d,1H, J ═ 8.5Hz),7.84(s,1H),7.75(d,1H, J ═ 2.6Hz),7.53 to 7.52(m,2H),7.42 to 7.39(m,2H),7.27 to 7.26(m,2H),7.16 to 7.09(m,2H),7.09 to 7.06(m,1H),5.90(d,1H, J ═ 2.8Hz),4.11(s, 2H).
Example 3
In this example, compound 30 as in table 1 above was prepared, differing from example 1 only in the following step (3):
(3) preparation of Compound 30
To a reaction flask were added 2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) aniline (0.29 g, 1 mmol), DCM (6 ml), triethylamine (0.13 ml), and o-tolylacetyl chloride (0.17 g, 1 mmol) in this order, and the mixture was stirred at room temperature for 16 hours. Water (50 ml) was added to the reaction mixture, and extraction was performed with DCM (50 ml), and the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.32 g of a yellow solid with a yield of 75.54%.
Process for preparation of Compound 301H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.39(d,1H, J ═ 8.1Hz),7.78(d,1H, J ═ 2.6Hz),7.75 to 7.70(m,1H),7.63 to 7.57(m,1H),7.57 to 7.50(m,2H),7.45 to 7.40(m,2H),7.24 to 7.16(m,3H),7.16 to 7.10(m,3H),7.10 to 7.03(m,1H),3.77(s,2H),2.29(s, 3H).
Example 4
In this example, compounds 32, 33, 34, 35, 37, 38 as in table 1 above were prepared by a method different from example 3 only in that o-tolylacetyl chloride used in step (3) was replaced with 3-chlorophenylacetyl chloride, 3-bromophenylacetyl chloride, 3-methylphenylacetyl chloride, 3-methoxyphenylacetyl chloride, 3-trifluoromethylphenylacetyl chloride, 4-fluorophenylacetyl chloride to prepare compounds 32, 33, 34, 35, 37, 38 in yields of 39.11%, 40.25%, 88.50%, 52.68%, 84.57%, 51.20%, respectively.
Process for preparation of compound 321H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.38(d,1H, J ═ 6.4Hz),7.84 to 7.77(m,2H),7.56 to 7.54(m,2H),7.43 to 7.41(m,2H),7.29 to 7.28(m,1H),7.20 to 7.15(m,5H),7.09 to 7.06(m,1H),5.90(s,1H),3.72(s, 2H).
Process for preparation of compound 331H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.36(d,1H, J ═ 6.4Hz),7.80 to 7.76(m,2H),7.54 to 7.52(d,2H, J ═ 10.2Hz),7.43 to 7.39(m,3H),7.33 to 7.31(d,1H, J ═ 6.4Hz),7.20 to 7.04(m,5H),5.88(s,1H),3.69(s,2H)
Process for preparation of compound 341H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.37(d,1H, J ═ 6.4Hz),7.75 to 7.65(m,2H),7.55 to 7.49(m,2H),7.43 to 7.37(m,2H),7.20 to 7.14(m,3H),7.13 to 7.07(m,3H),7.07 to 6.99(m,1H),5.77(d,1H, J ═ 2.6Hz),3.74(d,2H, J ═ 1.8Hz), and 2.27(d,3H, J ═ 3.6 Hz).
Process for preparation of compound 351H NMR(400MHz,CDCl3) The data are as follows: delta (ppm)8.38(d,1H, J ═ 6.4Hz),7.84 to 7.73(m,2H),7.54 to 7.52(m,2H),7.42 to 7.39(m,2H),7.19 to 7.15(m,3H),7.06 to 7.7.03(m,1H),6.86～6.81(m,2H),6.75～6.71(m,2H),5.83(d,1H,J＝2.6Hz),3.72(s,5H)。
Process for preparation of compound 371H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.40(d,1H, J ═ 8.1Hz),7.86(s,1H),7.78(d,1H, J ═ 2.6Hz),7.61 to 7.53(m,3H),7.51(t,2H, J ═ 4.0Hz),7.43(d,3H, J ═ 8.6Hz),7.21 to 7.14(m,2H),7.12 to 7.05(m,1H),5.91(d,1H, J ═ 2.7Hz),3.81(s, 2H).
Process for preparation of Compound 381H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)11.22(s,1H),8.46(d,1H, J ═ 8.7Hz),7.84(d,1H, J ═ 2.6Hz),7.79 to 7.75(m,1H),7.65 to 7.55(m,3H),7.53 to 7.48(m,2H),7.28 to 7.22(m,3H),7.07 to 6.99(m,1H),6.95(m,1H),6.17(d,1H, J ═ 4.1Hz,1H),3.93(s, 2H).
Example 5
In this example, compound 40 as in table 1 above was prepared, differing from example 1 only in the following step (3):
(3) preparation of Compound 40
To a reaction flask were added 2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) aniline (0.29 g, 1 mmol), DCM (6 ml), triethylamine (0.13 ml), and p-tolylacetyl chloride (0.17 g, 1 mmol) in this order, and the mixture was stirred at room temperature for 16 hours. Water (50 ml) was added to the reaction mixture, and extraction was performed with DCM (50 ml), and the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.31 g of a yellow solid with a yield of 74.82%.
Preparation of Compound 401H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.39(d,1H, J ═ 8.1Hz),7.89 to 7.80(m,1H),7.76(d,1H, J ═ 2.6Hz),7.57 to 7.53(m,2H),7.43(d,2H, J ═ 6.6Hz),7.17(d,4H, J ═ 8.1Hz),7.11 to 7.03(m,3H),5.84(d,1H, J ═ 2.6Hz),3.72(s,2H),2.27(s, 3H).
Example 6
Except for changing p-tolylacetyl chloride to p-methoxyphenylacetyl chloride in step (3) from example 5, compound 41 was prepared in 68.49% yield.
Process for preparation of Compound 411H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.37(d,1H, J ═ 6.4Hz),7.81(s,1H),7.73(d,1H, J ═ 2.0Hz),7.52(d,1H, J ═ 6.4Hz),7.40(d,1H, J ═ 7.2Hz),7.18 to 7.03(m,5H),6.78(d,2H, J ═ 6.8Hz),5.84(d,1H, J ═ 2.0Hz),3.70(s,2H),3.67(s, 3H).
Example 7
In this example, compound 44 as in table 1 above was prepared, differing from example 1 only in the following step (3):
(3) preparation of Compound 44
To a reaction flask were added 2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) aniline (0.29 g, 1 mmol), toluene (10 ml), potassium carbonate (0.55 g, 4 mmol), and p-cyanotolylacetyl chloride (0.18 g, 1 mmol) in this order, and the reaction solution was heated to reflux. After refluxing for 2.5 hours, the reaction mixture was cooled to room temperature, water (50 ml) was added to the reaction mixture, and extraction was performed with ethyl acetate (50 ml), the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.17 g of a yellow solid with a yield of 39.87%.
Process for preparation of compound 441H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.36(d,1H, J ═ 8.1Hz),7.92 to 7.77(m,2H),7.62 to 7.52(m,4H),7.50 to 7.39(m,4H),7.24 to 7.13(m,2H),7.13 to 7.05(m,1H),5.95(d,1H, J ═ 2.6Hz),3.81(s, 2H).
Example 8
Except for replacing p-cyanotolueneacetyl chloride with p-hydroxyphenylacetyl chloride in step (3) of example 7, compound 45 was prepared in 66.10% yield.
Process for preparation of Compound 451H NMR(400MHz,CDCl3) Data ofThe following were used: δ (ppm)8.35(d,1H, J ═ 8.0Hz),7.83(s,1H),7.72(d,1H, J ═ 2.6Hz),7.54 to 7.48(m,2H),7.43 to 7.36(m,2H),7.19 to 7.12(m,2H),7.11 to 7.02(m,3H),6.72 to 6.64(m,2H),5.83(d,1H, J ═ 2.6Hz),5.80(s,1H),3.65(s, 2H).
Example 9
In this example, compound 46 as in table 1 above was prepared, differing from example 1 only in the following step (3):
(3) preparation of Compound 46
To a reaction flask were added 2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) aniline (0.29 g, 1 mmol), toluene (10 ml), potassium carbonate (0.55 g, 4 mmol), and p-tolylacetyl chloride (0.23 g, 1 mmol) in this order, and the reaction solution was heated to reflux. After refluxing for 2.5 hours, the reaction mixture was cooled to room temperature, water (50 ml) was added to the reaction mixture, and extraction was performed with ethyl acetate (50 ml), the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 8: 1) to obtain 0.24 g of a yellow solid with a yield of 49.17%.
Process for preparation of compound 461H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.42(d,1H, J ═ 8.3Hz),7.87(s,1H),7.64(d,1H, J ═ 2.6Hz),7.53 to 7.48(m,4H),7.45 to 7.32(m,9H),7.23 to 7.13(m,2H),7.02 to 7.09(m,1H),5.80(d,1H, J ═ 2.6Hz),3.80(s, 2H).
Example 10
Except for the difference from example 7 in that p-phenyltolylacetyl chloride was replaced with 4- (pent-2-oxy) phenylacetyl chloride, 4-isopropoxyphenylacetyl chloride in step (3), respectively, to prepare compounds 47 and 48 in 26.76% yields, respectively.
Process for preparation of Compound 471H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.43 to 8.33(m,1H),7.83(s,1H),7.73(d,1H, J ═ 2.6Hz),7.55 to 7.48(m,2H),7.45 to 7.36(m,2H),7.19 to 7.12(m,4H),7.06 to 7.00(m,1H),6.82～6.76(m,2H),5.89～5.81(m,1H),4.32～4.24(m,1H),3.66(s,2H),1.72～1.63(m,2H),1.28～1.23(m,2H),1.22(d,3H,J＝6.0Hz),0.92(t,3H,J＝7.3Hz)。
Process for preparation of Compound 481H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.38(d,1H, J ═ 8.1Hz),7.82(s,1H),7.73(d,1H, J ═ 2.6Hz),7.57 to 7.50(m,2H),7.40(d,2H, J ═ 9.2Hz),7.19 to 7.11(m,4H),7.07 to 6.99(m,1H),6.81 to 6.74(m,2H),5.89 to 5.80(m,1H),4.44(q,1H, J ═ 5.74,6.1Hz),3.66(s,2H),1.27(d,6H, J ═ 6.0 Hz).
Example 11
In this example, compound 49 as in table 1 above was prepared as follows:
compound 45, i.e., N- (2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) phenyl) -2- (4-hydroxyphenyl) amide, was prepared using the same method as in example 8, and then compound 49 was prepared by the following reaction:
to a reaction flask were added N- (2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) phenyl) -2- (4-hydroxyphenyl) amide (0.21 g, 0.60 mmol), DMF (5 ml), cyclopropylmethyl bromide (0.10 g, 0.72 mmol), and potassium carbonate (0.10 g, 0.720 mmol) in this order, and the reaction was heated to reflux. After refluxing for 2 hours, the reaction mixture was cooled to room temperature, water (50 ml) was added to the reaction mixture, and extraction was performed with ethyl acetate (50 ml), the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.29 g of a yellow solid with a yield of 80.73%.
Process for preparation of compound 491H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)9.65(s,1H),8.54(d,1H, J ═ 8.0Hz),8.49 to 8.39(m,2H),7.81(d,1H, J ═ 2.6Hz),7.61 to 7.55(m,2H),7.43 to 7.37(m,2H),7.25 to 7.17(m,2H),7.10 to 7.15(m,1H),7.02 to 6.91(m,2H),6.10(d,1H, J ═ 2.6Hz),4.44(d,2H, J ═ 5.9Hz),3.90(s,2H),1.36 to 1.23(m,1H),0.72 to 0.65(m,2H),0.42 to 0.35(m,2H)。
Example 12
Except for the point that p-phenyltolylacetyl chloride was replaced with 4- (hept-2-yloxy) phenylacetyl chloride, 4-isopropoxyphenylacetyl chloride, respectively, in step (3), compound 50 was prepared in 22.38% yield.
Process for preparation of Compound 501H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)9.65(s,1H),8.54(d,1H, J ═ 8.0Hz),8.47 to 8.40(m,2H),7.81(d,1H, J ═ 2.6Hz),7.62 to 7.54(m,2H),7.43 to 7.36(m,2H),7.24 to 7.18(m,2H),6.98 to 6.90(m,2H),6.10(d,1H, J ═ 2.6Hz),4.30 to 4.35(m,1H),3.60(s,2H),1.77 to 1.61(m,4H),1.47 to 1.21(m,4H),0.96(t,3H, J ═ 7.4Hz),0.90(t,3H, J ═ 7.0 Hz).
Example 13
Compound 45, i.e., N- (2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) phenyl) -2- (4-hydroxyphenyl) amide, was prepared using the same method as in example 8, and then compound 51 was prepared by the following reaction:
to a reaction flask were added N- (2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) phenyl) -2- (4-hydroxyphenyl) amide (0.34 g, 0.86 mmol), DMF (5 ml), 3-chloro-4-fluorotrifluoromethyl (0.21 g, 1.04 mmol), and potassium carbonate (0.10 g, 1.04 mmol) in this order, and the reaction solution was heated to reflux. After refluxing for 2 hours, the reaction mixture was cooled to room temperature, water (50 ml) was added to the reaction mixture, and extraction was performed with ethyl acetate (50 ml), the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.41 g of a yellow solid with a yield of 78.76%.
Process for preparation of Compound 511H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)9.63(s,1H),8.53(d,1H, J ═ 8.0Hz),8.49 to 8.37(m,2H),7.82(d,2H, J ═ 2.6Hz),7.62 to 7.51(m,2H),7.46 to 7.36(m,4H),7.24 to 7.18(m,2H),7.16 to 7.11(m,1H),6.94 to 6.88(m,2H),6.11(d, 1H), and,J＝2.6Hz),3.63(s,2H)。
example 14
In this example, compounds 52, 53, 54 and 55 as in table 1 above were prepared in yields of 52.30%, 48.60%, 61.32% and 82.30%, respectively, except that the o-fluorobenzeneacetyl chloride used in step (3) was replaced with 2, 3-dichlorophenylacetyl chloride.
Process for preparation of Compound 521H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)9.63(s,1H),8.53(d,1H, J ═ 8.0Hz),8.49 to 8.37(m,2H),7.82(d,2H, J ═ 2.6Hz),7.62 to 7.51(m,2H),7.46 to 7.36(m,4H),7.24 to 7.18(m,2H),7.16 to 7.11(m,1H),6.94 to 6.88(m,2H),6.11(d,1H, J ═ 2.6Hz),3.63(s, 2H).
Process for preparation of compound 531H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.37(d,1H, J ═ 6.4Hz),7.88(s,1H),7.79(d,1H, J ═ 2.0Hz),7.56 to 7.54(m,2H),7.43 to 7.40(m,2H),7.31 to 7.28(m,3H),7.21 to 7.16(m,3H),7.10 to 7.07(m,1H),5.92(d,1H, J ═ 2.6Hz),3.84(s, 2H).
Process for preparation of compound 541H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.36(d,1H, J ═ 6.4Hz),7.88(s,1H),7.75(d,1H, J ═ 2.0Hz),7.54 to 7.52(m,2H),7.43 to 7.40(m,2H),7.31 to 7.28(m,3H),7.21 to 7.16(m,3H),7.10 to 7.07(m,1H),5.92(d,1H, J ═ 2.6Hz),3.89(s, 2H).
Process for preparation of Compound 551H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)9.84(s,1H),8.47(d,1H, J ═ 2.7Hz),7.98 to 7.86(m,1H),7.79 to 7.70(m,2H),7.57 to 7.47(m,2H),7.40(q,1H),7.33(d,2H, J ═ 2.0Hz),7.23 to 7.10(m,3H),6.10(d,1H, J ═ 2.7Hz),3.75(s, 2H).
Example 15
In this example, compound 56 as in table 1 above was prepared, differing from example 1 only in the following step (3):
(3) preparation of Compound 56
To a reaction flask were added 2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) aniline (0.29 g, 1 mmol), toluene (10 ml), potassium carbonate (0.55 g, 4 mmol), and p-3, 5 difluorophenylacetyl chloride (0.19 g, 1 mmol) in that order, and the reaction was heated to reflux. After refluxing for 2 hours, the reaction mixture was cooled to room temperature, water (50 ml) was added to the reaction mixture, and extraction was performed with ethyl acetate (50 ml), the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.356 g of a brown solid with a yield of 80.94%.
Process for preparation of compound 561H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.37(d,1H, J ═ 8.0Hz),7.83(s,1H),7.72(d,1H, J ═ 2.6Hz),7.54 to 7.48(m,2H),7.43 to 7.36(m,2H),7.19 to 7.12(m,2H),7.11 to 7.02(m,3H),6.72 to 6.64(m,2H),5.83(d,1H, J ═ 2.6Hz),5.80(s,1H),3.65(s, 2H).
Example 16
In this example, compounds 61 and 70 as in table 1 above were prepared, differing from example 1 only in the following step (3):
(3) preparation of Compound 61
To a reaction flask were added 2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) aniline (0.29 g, 1 mmol), DCM (6 ml), triethylamine (0.13 ml), and 3,4, 5-trimethoxyphenylacetyl chloride (0.24 g, 1 mmol) in this order, and the mixture was stirred at room temperature for 16 hours. Water (50 ml) was added to the reaction mixture, and extraction was performed with DCM (50 ml), and the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.22 g of a brown solid with a yield of 43.70%.
Process for preparation of compound 611H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.39(d,1H, J ═ 8.0Hz),7.93(s,1H),7.74(d,1H, J ═ 2.6Hz),7.55 to 7.49(m,2H),7.41 to 7.36(m,2H),7.17 ℃. (c)7.12(m,2H),7.00～7.00(m,1H),6.49(s,2H),5.86(d,1H,J＝2.6Hz),3.77(s,9H),3.68(s,3H)。
(3) Preparation of Compound 70
To a reaction flask were added 2- ((1- (4-chlorophenyl) -1H-pyrazol-3-yl) oxy) aniline (0.29 g, 1 mmol), DCM (6 ml), triethylamine (0.13 ml), and 1-naphthylacetyl chloride (0.20 g, 1 mmol) in this order, and the mixture was stirred at room temperature for 16 hours. Water (50 ml) was added to the reaction mixture, and extraction was performed with DCM (50 ml), and the organic layer was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: PE: EA ═ 10: 1) to obtain 0.25 g of a yellow liquid with a yield of 62.95%.
Process for preparation of Compound 701H NMR(400MHz,CDCl3) The data are as follows: δ (ppm)8.37(d,1H, J ═ 8.0Hz),7.97(d,1H, J ═ 8.0Hz),7.75 to 7.65(m,3H),7.52 to 7.37(m,10H),7.15 to 6.98(m,3H),5.46(d,1H, J ═ 2.6Hz),4.17(s, 2H).
Example 17
In this example, the bactericidal activity of the prepared acetamide compound was measured, and the compound of the present invention was used to test various plant diseases. The method of testing is as follows:
the test was performed using potted seedling assay. Selecting potted cucumber seedlings with consistent growth in two leaf stages as test host plants of cucumber downy mildew; selecting potted wheat seedlings with consistent growth in two leaf periods as test host plants of wheat powdery mildew, and selecting potted corn seedlings with consistent growth in two leaf periods as test host plants of corn rust. Foliar spray treatments were carried out with the compounds of the present invention at the designed concentrations. And additionally arranging a blank control sprayed with clear water, repeating for 3 times, and performing disease inoculation the next day after treatment. After inoculation, the plants are placed in a climatic chamber for humid cultivation (temperature: 25 ℃ day, 20 ℃ night, relative humidity: 95-99%). After the test material is cultured for 24h, the test material is moved to a greenhouse for culture, and plants which do not need to be subjected to moisture-preserving culture are directly inoculated and cultured in the greenhouse. The control is taken to evaluate the disease prevention effect of the compound after full disease (usually a week). The results were examined with reference to the American society for Plant Diseases, A Manual of Association, expressed as 100-0, with "100" representing no disease and "0" representing the most severe degree of disease.
Some of the test results are as follows:
prevention effect on cucumber downy mildew:
according to the test method, in some tested compounds, the following compounds have better control effect at the concentration of 400ppm, and the control effect is more than 50 percent: compounds 33, 37, 40, 41, 44 and 46.
The control effect on cucumber powdery mildew is as follows:
according to the test method, in some tested compounds, the following compounds have better control effect at the concentration of 400ppm, and the control effect is more than 50 percent: compounds 37, 40, 44, 46 and 56.
Prevention of soybean rust:
according to the test method, in some tested compounds, the following compounds have better control effect at the concentration of 100ppm, and the control effect is more than 50 percent: compounds 25, 33 and 41.
The present invention is illustrated by the above examples, but the present invention is not limited to the above examples, that is, the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (31)
1. An acetamide compound characterized by having the structure shown in formula I:
wherein Q is1Selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, Q2Selected from substituted or unsubstituted aryl;
the substituent in the substituted aryl or the substituted heteroaryl is halogen atom, C1-C6 alkyl, C1-C6 haloalkyl, C1-C7 alkoxy, C1-C7 haloalkoxy, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 cycloalkylmethyl, C3-C6 halocycloalkylmethyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C4 alkylamino, di-C1-C4 alkylamino, cyano, nitro, hydroxyl, phenyl, phenoxy or halophenoxy;
the aryl is phenyl, naphthyl or tetrahydronaphthyl;
the heteroaryl group is pyridyl, pyridine-N-oxyl, pyrimidinyl, pyridazinyl, pyrazinyl, furyl, thienyl, quinolyl, tetrahydroquinolyl, benzofuryl or indolyl;
R1selected from hydrogen, C1-C6 alkyl, C1-C6 alkylcarbonyl or C1-C6 alkoxycarbonyl.
2. The acetamide compound of claim 1 wherein R1Selected from hydrogen, C1-C6 alkyl or C1-C6 alkylcarbonyl.
3. The acetamide compound of claim 1 wherein Q2Selected from phenyl or para-substituted phenyl.
4. The acetamide compound of claim 1 wherein Q2Selected from phenyl, p-fluorophenyl, p-chlorophenyl or p-bromophenyl.
5. The acetamide compound of claim 1, wherein the acetamide compound is any one of the following compounds:
6. the salt of an acetamide compound of claims 1 to 5 wherein the salt of an acetamide compound is an inorganic or organic salt of the acetamide compound.
7. The salt of acetamide compound of claim 6 wherein the inorganic salt is any one of or a combination of at least two of the hydrochloride, sulfate, nitrate, bicarbonate, carbonate, or phosphate salts.
8. The salt of acetamide compound of claim 6 wherein the organic salt is any one of or a combination of at least two of formate, acetate, trifluoroacetate, benzenesulfonate, p-toluenesulfonate, methanesulfonate, benzoate, citrate, malate, tartrate, maleate, succinate, ascorbate or oxalate.
9. The process for the preparation of acetamide compound according to any one of claims 1 to 5, wherein the process is:
when the acetamide compound is shown as R in the general formula I1When hydrogen is used: reacting a compound shown as a formula II with a compound shown as a formula III to obtain an acetamide compound shown as a formula I-A, wherein the reaction formula is as follows:
when the acetamide compound is shown as R in the general formula I1When hydrogen is not present: reacting the acetamide compound shown in the formula I-A with a compound shown in the formula IV to obtain an acetamide compound shown in the formula I-B, wherein the reaction formula is as follows:
wherein LG represents a leaving group.
10. The preparation method according to claim 9, wherein the molar ratio of the compound represented by the formula II to the compound represented by the formula III is 1:1 to 3: 1.
11. The method of claim 9, wherein R is in the formula I1And when the hydrogen is used, the solvent for the reaction is any one or the combination of at least two of dichloromethane, chloroform, hexane, carbon tetrachloride, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide.
12. The method of claim 9, wherein R is in the formula I1In the case of hydrogen, the reaction is carried out in the presence of a basic substance, which is an organic or inorganic base.
13. The method according to claim 12, wherein the organic base is any one or a combination of at least two of triethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide.
14. The method according to claim 12, wherein the inorganic base is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or sodium hydride, or a combination of at least two of them.
15. The method of claim 9, wherein R is in the formula I1In the case of hydrogen, the reaction temperature is not lower than-10 ℃ and not higher than the boiling point of the reaction solvent.
16. According to claimThe preparation method is characterized in that R in the general formula I of the acetamide compound1In the case of hydrogen, the reaction time is from 0.5 to 48 hours.
17. The preparation method according to claim 9, wherein the molar ratio of the acetamide compound of formula I-A to the compound of formula IV is 1:1 to 1: 3.
18. The method of claim 9, wherein R is in the formula I1When not hydrogen, the solvent for the reaction is any one or a combination of at least two of dichloromethane, chloroform, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide.
19. The method of claim 9, wherein R is in the formula I1In the absence of hydrogen, the reaction is carried out in the presence of a basic substance, which is an organic or inorganic base.
20. The method according to claim 19, wherein the organic base is any one or a combination of at least two of triethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide.
21. The method of claim 19, wherein the inorganic base is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or sodium hydride, or a combination of at least two of them.
22. The method of claim 9, wherein R is in the formula I1When not hydrogen, the reaction temperature is not lower than-10 ℃ and not higher than the boiling point of the reaction solvent.
23. The method of claim 9, wherein R is in the formula I1In the absence of hydrogen, the reaction time is from 0.5 to 48 hours.
24. The production method according to claim 9, wherein LG is a chlorine atom or a bromine atom.
25. Use of the acetamide compound according to any one of claims 1 to 5 for the control of plant diseases.
26. Use according to claim 25, wherein the plant disease is soybean rust, cucumber downy mildew or cucumber powdery mildew.
27. A bactericide composition, which comprises an active ingredient which is the acetamide compound of any one of claims 1 to 5 or the salt thereof of any one of claims 6 to 8, and an agriculturally pharmaceutically acceptable carrier.
28. The germicidal composition of claim 27, wherein the active ingredients are present in the germicidal composition in an amount of 1 to 99% by weight.
29. A method for controlling plant diseases, comprising: applying an effective amount of the fungicidal composition of claim 27 or 28 to a medium in which a plant disease or its growth is to be controlled.
30. The method for controlling plant diseases according to claim 29, wherein the effective dose is 10 to 1000g per hectare.
31. The method for controlling plant diseases according to claim 30, wherein the effective dose is 20 to 500g per hectare.
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| CN1033457A (en) * | 1987-06-08 | 1989-06-21 | 孟山都公司 | 3-(4-nitrophenoxy) pyrazoles that replaces and as the purposes of weedicide |
| WO2013025897A1 (en) * | 2011-08-16 | 2013-02-21 | Georgetown University | Methods of treating bacterial infections with 1,2-benzisothiazolinone and isoindolinone derivatives |
| WO2014138833A1 (en) * | 2013-03-13 | 2014-09-18 | União Brasileira De Educação E Assistência , Mantenedora Da Pucrs | Compounds, use, pharmaceutical composition for inhibiting reductase in microorganisms, inha binder and method for obtaining inha binders |
| CN106699732A (en) * | 2016-11-18 | 2017-05-24 | 安徽农业大学 | Preparation of pyrazole nicotinamide compound and application thereof as bactericide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033457A (en) * | 1987-06-08 | 1989-06-21 | 孟山都公司 | 3-(4-nitrophenoxy) pyrazoles that replaces and as the purposes of weedicide |
| WO2013025897A1 (en) * | 2011-08-16 | 2013-02-21 | Georgetown University | Methods of treating bacterial infections with 1,2-benzisothiazolinone and isoindolinone derivatives |
| WO2014138833A1 (en) * | 2013-03-13 | 2014-09-18 | União Brasileira De Educação E Assistência , Mantenedora Da Pucrs | Compounds, use, pharmaceutical composition for inhibiting reductase in microorganisms, inha binder and method for obtaining inha binders |
| CN106699732A (en) * | 2016-11-18 | 2017-05-24 | 安徽农业大学 | Preparation of pyrazole nicotinamide compound and application thereof as bactericide |
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